Effect of hydrogen bonding on the rheology of polycarbonate/organoclay nanocomposites

The linear dynamic viscoelastic properties and non-linear transient rheology of polycarbonate (PC)/clay nanocomposites were investigated at temperatures ranging from 240 to 280 °C. For the study, nanocomposites of PC and natural montmorillonite (Cloisite Na⁺) or chemically modified clay (Cloisite 30B) were prepared by melt blending in a twin-screw extruder. Cloisite 30B is a natural montmorillonite modified with methyl, tallow, bis-2-hydroxyethyl, quaternary ammonium chloride (MT2EtOH). In both PC/Cloisite Na⁺ and PC/Cloisite 30B nanocomposites the concentration of clay was varied from 2.3 to 4.3 wt%. In situ Fourier transform infrared (FTIR) spectroscopy results show that at temperatures ranging from 30 to 280 °C the carbonyl groups in PC and the hydroxyl groups in MT2EtOH of Cloisite 30B in PC/Cloisite 30B nanocomposites formed hydrogen bonds, while no evidence of hydrogen bonding was observed in the PC/Cloisite Na⁺ nanocomposites. There are no discernible sharp reflections in the X-ray diffraction (XRD) patterns of PC/Cloisite 30B nanocomposites, after Cloisite 30B having the d₀₀₁ spacing of 1.85 nm was mixed with PC, whereas the d₀₀₁ spacing changes little (1.17 nm) before and after the mixing of Cloisite Na⁺ to PC. Transmission electron microcopy (TEM) images show that organoclay platelets are well dispersed in PC/Cloisite 30B nanocomposites, while the untreated clay platelets are poorly dispersed in PC/Cloisite Na⁺ nanocomposites. The observed differences in XRD patterns and TEM images between the two nanocomposite systems are explained by in situ FTIR spectroscopy. The results of rheological measurements (linear dynamic viscoelasticity, non-linear transient shear flow, and steady-state shear flow) support the conclusions drawn from the results of XRD, TEM, and FTIR spectroscopy.     

Supercritical CO2 dispersion of nano-clays and clay/polymer nanocomposites

Dispersed polymer/clay nanocomposites are of great interest because they can significantly improve the properties of existing polymeric materials. However, achieving a high level of clay dispersion has been a key challenge in the production of polymer/clay nanocomposites. In this paper, we explore a novel supercritical carbon dioxide (scCO₂) processing method that utilizes scCO₂ to disperse nano-clays. The structure and properties of the clays and the resultant nanocomposites are characterized using a combination of wide-angle X-ray diffraction (WAXD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and rheology. Significant dispersion was achieved with dry Cloisite 93A clay, whereas relatively poor dispersion was achieved with dry Cloisite Na⁺ (natural clay). The extent of clay dispersion appears to be dependent on the ‘CO₂-philicity’, which in turn appears to depend on the surface modifications and inter-gallery spacing. The presence of an acidic hydrogen on the surfactant in Cloisite 93A appears to play a strong role in its ‘CO₂-philicity’. The ability to delaminate dry clays is significant because it will likely increase the ability to produce dispersed clay/polymer nanocomposites via melt processing. In addition to delaminating dry clays, we demonstrate that CO₂-phobic Cloisite Na⁺ (natural clay) can be partially dispersed with scCO₂, using a CO₂-philic polymer, polydimethylsiloxane (PDMS). The dispersed clay/PDMS nanocomposite shows an order of magnitude increase in the dynamic storage modulus at low frequencies, accompanied by the emergence of a ‘solid-like’ plateau, characteristic of dispersed nanocomposites with enhanced clay/polymer interactions.     

Ion-dipole interactions in the dispersion of organoclay nanocomposites based on polystyrene-block-poly(2-vinylpyridine) copolymer

The dispersion characteristics of organoclay nanocomposites based on polystyrene-block-poly(2-vinylpyridine) (S2VP diblock) copolymer were investigated using transmission electron microscopy (TEM), X-ray diffraction (XRD), and solid-state nuclear magnetic resonance (NMR) spectroscopy. For the investigation, S2VP diblock copolymers having three different compositions were synthesized via sequential anionic polymerization. Each S2VP diblock copolymer was used to prepare nanocomposites by solution blending with natural clay (montmorillonite, MMT) or commercial organoclays (Cloisite 30B, Cloisite 10A, Cloisite 15A, and Cloisite 25A from Southern Clay Products). All four organoclays employed were treated with a surfactant having quaternary ammonium salt with N⁺ ion. It was found, via TEM and XRD, that the nanocomposites with MMT show very poor dispersion characteristics regardless of block copolymer composition. However, the block copolymer composition was found to have a profound influence on the dispersion characteristics of the nanocomposites with an organoclay. Specifically, the nanocomposites based on S2VP-5 having 5 wt% poly(2-vinylpyridine) (P2VP) block gave rise to a very high degree of dispersion, irrespective of the chemical structure of the surfactant residing at the surface of the organoclay employed, whereas the dispersion characteristics of the nanocomposites became progressively poorer as the amount of P2VP block in an S2VP diblock copolymer increased from 5 to 25 wt% and to 56 wt%. The observed dispersion characteristics were explained by hypothesizing the presence of ion-dipole interactions between the positively charged N⁺ ions in the surfactant residing at the surface of the organoclay nanoparticles and the dipoles in the P2VP block of S2VP diblock copolymers. The validity of this hypothesis was confirmed using solid-state NMR spectroscopy, by determining the dependence of the composition of S2VP diblock copolymer on the extent of ion-dipole interactions and thus on the dispersion characteristics of the nanocomposites prepared.     

Nanostructure and dynamic mechanical properties of silane-functionalized montmorillonite/epoxy nanocomposites

In this work sodium montmorillonite (Na-MMT) was functionalized with N-(2-aminoethyl)-3-aminopropyl-trimethoxysilane and the corresponding silylated clay was used to modify epoxy matrix cured with triethylenetetramine. The grafting/intercalation of the aminosilane inside the clay galleries were followed by infrared spectroscopy, X-ray diffraction, thermogravimetric analysis and ²⁹Si cross-polarization magic-angle-spinning nuclear magnetic-resonance (CP/MAS NMR) spectroscopy. Epoxy-based nanocomposites were prepared with different amounts of silylated clay or commercial organoclay, Cloisite 30B, whose intercalating agent consists of a methyl, tallow, bis-2-hydroxyethyl quaternary ammonium salt. The degree of intercalation/exfoliation was estimated by X-ray diffraction experiments and confirmed by small angle X-ray scattering. Nanocomposites prepared with silylated clay displayed no peak in both XRD and SAXS curves whereas those prepared with Cloisite 30B exhibited a clear interference peak corresponding to an interlayer spacing d₀₀₁ of 4.1 nm. The former also presented a better dispersion, with a high proportion of tactoids smaller than 2 nm, as estimated by SAXS. From the results of dynamic mechanical analysis it was observed that most of the nanocomposites display higher storage modulus mainly at temperatures above the glass transition temperature. The glass transition temperature is similar or higher than the neat epoxy network for nanocomposites containing 1 wt.% of silylated clay or higher.     

Effect of Clay Types on the Mechanical,Dynamic Mechanical and Morphological Properties of Polypropylene Nanocomposites

In the present investigation Polypropylene–Maleic anhydride grafted polypropylene–organically modified MMT (PP-MAPP-OMMT) nanocomposites were prepared by melt mixing in a twin screw extruder followed by injection molding. The effect of clay chemistry and compatibilizer on the properties of the nanocomposites has been studied. Sodium montmorillonite has been organically modified using quaternary and alkyl amine intercalants. A comparative account with commercial quaternary ammonium modified clays i.e Cloisite 20A, Cloisite 15A and Cloisite 30B has been presented. Storage modulus of PP matrix also increased in the nanocomposites, indicating an increase in the stiffness of the matrix polymer with the addition of organically modified nanoclays. The morphology of the nanocomposites has been examined using wide angle X-ray diffraction (WAXD) and transmission electron microscopy (TEM). Morphological findings revealed efficient dispersion of organically modified nanoclays within the PP matrix. MAPP compatibilized PP/Cloisite 15A nanocomposites displayed finely dispersed exfoliated nanomorphology as compared with other systems.     

Optimization of processing parameters for the synthesis of low‐density polyethylene/organically modified montmorillonite nanocomposites using X‐ray diffraction with experimental design

The influence of the processing parameters on the synthesis of low‐density polyethylene (LDPE)/organically modified montmorillonite (OMM) nanocomposite films was studied using experimental design. Intercalation in the nanocomposites was analysed using X‐ray diffraction and verified using atomic force microscopy. Four direct melt processing parameters were studied to obtain surface maps of intercalation in the nanocomposites: concentration of OMM (clay‐%), concentration of Polybond^® 3149 (compatibilizer‐%), mixing temperature (T_mix) and mixing time. An ANOVA validated the polynomial function, and intercalation maps from response surface methodology (RSM) were obtained. The clay‐% parameter had the most significant effect, and T_mix showed no significant effect on intercalation (p < 0.05). A strong synergic interaction between clay‐% and compatibilizer‐% was observed, which is not possible to detect using univariate experiments. RSM provides a powerful tool for choosing the best processing conditions that lead to formulations with the highest intercalations by considering the main factors and their interactions. © 2013 Society of Chemical Industry     

The use of nanoclay in preparation of epoxy anticorrosive coatings

Epoxy/clay nanocomposites (NC) have become a very interesting topic among researchers in the past two decades because nanoclays have a positive effect on the mechanical, thermal and especially barrier and anticorrosive performances of the polymers. In this study epoxy NCs and NC-based epoxy coatings were prepared by the solution intercalation method using Cloisite 30B as nanoclay. WAXD and SEM analyses revealed that a mainly exfoliated structure was obtained in epoxy NC with 1 wt% clay content, while higher clay loadings reduced the number of exfoliated clay nanolayers and produced a mainly intercalated structure. EIS, TGA and DMA analyses showed that epoxy NCs with clay content below 5 wt% exhibited increased corrosion stability, thermal stability, glass transition temperature (T_g) and storage modulus (G′), in both glassy and rubbery states due to the nanoscale dispersion of Cloisite 30B and the barrier effect of individual nanolayers. Enhanced mechanical properties were also noticed at higher clay loadings, but the rate of improvement was lower. The highest extent of exfoliation and the most homogeneous macromolecular network was found for NC with 1 wt% of clay, leading to the highest improvement of thermal and anticorrosive properties. The salt spray test results showed that anticorrosive properties of epoxy coatings in the presence of 3 wt% and especially 1 wt% of Cloisite 30B were significantly better, thus indicating that nanoclay efficiently modifies the commercial epoxy coatings.     

Impact of acid containing montmorillonite on the properties of Nafion membranes

The counter-ions of montmorillonite have been exchanged for ammonium cations containing either a sulfonic acid or a carboxylic acid in order to improve the performances of sulfonated membranes in direct methanol fuel cell. These layered silicates have been dispersed within Nafion^® by solution mixing. Comparison with conventional organo-modified montmorillonite (Cloisite 30B) shows that the incorporation of carboxylic acid in the clay galleries improves the filler dispersion and, consequently, the methanol barrier properties. Moreover, the negative impact of Cloisite 30B on the ionic conductivity is restricted.     

Effect of nanofillers as reinforcement agents for lignin composite fibers

Biobased nanocomposites and composite fibers were prepared from organosolv lignin/organoclay mixtures by mechanical mixing and subsequent melt intercalation. Two organically‐modified montmorillonite (MMT) clays with different ammonium cations were used. The effect of organoclay varying from 1 to 10 wt % on the mechanical and thermal properties of the nanocomposites was studied. Thermal analysis revealed an increased in T_g for the nanocomposites as compared with the original organosolv lignin. For both organoclays, lignin intercalation into the silicate layers was observed using X‐ray diffraction (XRD). The intercalated hybrids exhibited a substantial increase in tensile strength and melt processability. In the case of organoclay Cloisite 30B, X‐ray analysis indicates the possibility of complete exfoliation at 1 wt % organoclay loading. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of epoxy based nanocomposites

Epoxy‐clay nanocomposites were synthesized to examine the effects of the content and type of different clays on the structure and mechanical properties of the nanocomposites. Diglycidyl ether of bisphenol‐A (epoxy) was reinforced by 0.5–11 wt % natural (Cloisite Na⁺) and organically modified (Cloisite 30B) types of montmorillonite. SEM results showed that as the clay content increased, larger agglomerates of clay were present. Nanocomposites with Cloisite 30B exhibited better dispersion and a lower degree of agglomeration than nanocomposites with Cloisite Na⁺. X‐ray results indicated that in nanocomposites with 3 wt % Cloisite 30B, d‐spacing expanded from 18.4 Å (the initial value of the pure clay) to 38.2 Å. The glass transition temperature increased from 73°C, in the unfilled epoxy resin, to 83.5°C in the nanocomposite with 9 wt % Cloisite 30B. The tensile strength exhibited a maximum at 1 wt % modified clay loading. Addition of 0.5 wt % organically modified clay improved the impact strength of the epoxy resin by 137%; in contrast, addition of 0.5 wt % unmodified clay improved the impact strength by 72%. Tensile modulus increased with increasing clay loading in both types of nanocomposites. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1081–1086, 2005     

Analysis of the structure and mass transport properties of nanocomposite polyurethane

In this work, nanocomposite adhesives obtained using an organically modified montmorillonite (OMM) in a polyurethane matrix were studied. The basal distance of OMM before and after mixing with the polyol and after curing was characterized by X‐Ray diffraction. The viscosity of polyols‐OMM systems was studied as function of shear rate in a cone‐plate rheometer in order to correlate the viscosity with the aggregation state of OMM. A simple model accounting for an apparent increase of rheological units size associated with the intercalation of macromolecules into OMM galleries is proposed. Curing was performed at room temperature for 1 week. The basal distances of crosslinked PU nanocomposites were obtained by X‐ray diffraction. The glass transition temperature, T_g, of PU nanocomposites, as measured using differential scanning calorimetry, increases with increasing volume fraction of OMM. Finally, the permeability to oxygen and water vapor of polyurethane clay‐nanocomposites was measured. The gas permeation through the composites was correlated to the volume fraction of the impermeable inorganic part of the OMM. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Biodeterioration of plasticized PVC/montmorillonite nanocomposites in aerobic soil environment

The aim of this study was to assess the effect of montmorillonite nanofillers, Cloisite Na⁺ and Cloisite 30B, on the biodeterioration of PVC-based nanocomposites plasticized by means of dioctyl adipate (DOA), dioctyl phthalate (DOP) and modified poly(propylene adipate) (PPA), in the aerobic environment of soil (soil burial test, time of exposure: 198 days). Tests were carried out at 25 ± 1 °C, under moisture-controlled (55 %) and aerobic conditions. The extent of the biodeterioration process was evaluated on the basis of changes in weight, tensile strength and elongation-at-break values. Finally, analysing chemical structures using FTIR and visual observation, both macroscopic and microscopic via scanning electron microscopy assisted in the evaluation process. The results of this study suggested that plasticized PVC/montmorillonite nanocomposites have an increased susceptibility for undergoing biological deterioration in comparison with plasticized PVC. In each instance, adding Cloisite 30B resulted in reducing the resistance of PVC/montmorillonite nanocomposites to the actions of microorganisms. In the case of Cloisite Na⁺ as the filler, results cannot be clearly quantified, although a negative influence prevailed, particularly a change in colour, whose change intensity was also dependent on the type of plasticizer, increasing in the following sequence: PVC/DOA/Cloisite Na⁺ > PVC/DOP/Cloisite Na⁺ > PVC/PPA/Cloisite Na⁺. However, each sample containing Cloisite Na⁺ achieved a lower rate of degradation (by normalised weight loss and FTIR) compared with nanocomposites containing Cloisite 30B. This can be attributed to the migration and accumulation of Cloisite Na⁺ on the surface of the nanocomposites particles where the former phenomenon producing a surface barrier which caused a reduction in the permeability of the material toward water and microorganisms, during the test.     

Preparation and characterization of PET/clay nanocomposites by melt compounding

Poly(ethylene terephthalate) (PET) nanocomposites were prepared via melt compounding using a twin‐screw extruder at 265°C. Three different types of organomodified clay were melt compounded with PET: a commercial ammonium‐modified silicate clay (Cloisite 30B) and specially prepared thermally stable phosphonium‐ and imidazolium‐modified montmorillonites. X‐ray diffraction, scanning electron microscopy, transmission electron microscopy (TEM), and thermogravimetric analysis were used to characterize and evaluate the quality of the nanocomposites. To obtain quantitative evaluation of the dispersion level in nanocomposites, statistical analysis of TEM micrographs was performed using a dispersion parameter, D_0.1, based on free‐path spacing measurements. The results showed that the ammonium surfactant yielded the best intercalation results in nanocomposites. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Polybutadiene rubber/organoclay nanocomposites: Effect of organoclay with various modifier concentrations on the vulcanization behavior and mechanical properties

It has been reported that the cure time t₉₀, scorch time t₂, and their difference (t₉₀?t₂) of Polybutadiene rubber (BR)/organoclay nanocomposites were much reduced over those of BR. This effect can be attributed to the ammonium groups in the organoclay. The possible formation of a Zn complex in which sulfur and ammonium modifier participate may facilitate the formation of crosslinks. If this assumption is true, it is expected that the organoclay with higher ammonium modifier concentration will give larger torque difference and faster vulcanization rate to the BR/organoclay nanocomposites. The effect of organoclay with different modifier concentration on the vulcanization behavior and mechanical properties of BR/organoclay hybrid was investigated in this study. As expected, the order of the torque difference was BR/Cloisite 15A > BR/Cloisite 10A > BR/Cloisite 20A > BR/Cloisite 25A > BR/Cloisite 30B > BR/Cloisite Na⁺, and the order of vulcanization rate also showed similar trends. The organoclay with higher modifier concentration gave larger torque difference and faster vulcanization rate to the BR/organoclay nanocomposites. POLYM. ENG. SCI., 47:308–313, 2007. © 2007 Society of Plastics Engineers.     

Preparation and characterization of high performance exfoliated montmorillonite/silicone rubber nanocomposites with enhanced mechanical properties

Highly exfoliated and intercalated silicone rubber (SR) nanocomposites based on natural montmorillonite (Cloisite Na⁺) and organically modified montmorillonite (Cloisite 30B and Cloisite 20A) were successfully prepared by melt‐mixing technique. Dispersion of the nanoclays in the rubber nanocomposites was subsequently investigated. As indicated by the X‐ray diffraction (XRD) analysis, intercalation, and exfoliation of the clay particles in the nanocomposites was achieved at less than 8 parts per hundred (phr) rubber by weight, irrespective of the initial interlayer spacing of the nanoclay particles. Both Cloisite Na⁺ and Cloisite 30B were spontaneously transformed into exfoliated microstructures during the vulcanisation stage. Overall, the use of the nanoclays in silicone rubber improved the Young's modulus, tensile strength, and elongation at break by more than 50% as compared with the control rubber. In addition, this work provided a fresh insight into the way intercalated and exfoliated morphologies affect mechanical properties of silicone rubber nanocomposites. It was shown that the exfoliated Cloisite Na⁺ yielded outstanding mechanical properties with low hysteresis at the same loading of the exfoliated Cloisite 30B and intercalated Cloisite 20A organoclays. As expected, the formation of crosslinks affected the mechanical properties of the rubber vulcanizate significantly. POLYM. ENG. SCI., 53:2603–2614, 2013. © 2013 Society of Plastics Engineers     

Dispersion characteristics and rheology of organoclay nanocomposites based on a segmented main-chain liquid-crystalline polymer having side-chain azopyridine with flexible spacer

The dispersion characteristics and rheology of organoclay nanocomposites based on a main-chain liquid-crystalline polymer having side-chain azopyridine with flexible spacer (PABP) were investigated using X-ray diffraction (XRD), transmission electron microscopy (TEM), and oscillatory shear rheometry. In the preparation of nanocomposites via solution blending under vigorous stirring, two commercial organoclays (Southern Clay Products) were employed: one (Cloisite 30B) treated with a surfactant (MT2EtOH) having hydroxyl groups, and the other (Cloisite 20A) treated with a nonpolar surfactant (2M2HT) having hydrogenated tallow. Also prepared, for comparison, were nanocomposites prepared by mixing PABP with natural clay (montmorillonite, MMT). The following observations were made. (i) PABP/Cloisite 30B nanocomposite has featureless XRD patterns and a very high degree of dispersion of Cloisite 30B aggregates as determined from TEM. (ii) PABP/Cloisite 20A nanocomposite has shown a conspicuous XRD reflection peak and intercalation of Cloisite 20A aggregates as determined from TEM. (iii) PABP/MMT nanocomposite has shown XRD patterns, which are virtually the same as the XRD patterns of neat PABP with a slightly increased gallery distance, and it has very poor dispersion of MMT aggregates in the matrix of PABP. The observed high degree of dispersion of Cloisite 30B aggregates in PABP/Cloisite 30B nanocomposite is attributable to the formation of hydrogen bonds between the pyridyl group of side-chain azopyridine and the hydroxyl groups in the surfactant MT2EtOH residing at the surface of Cloisite 30B. The presence of hydrogen bonds in the PABP/Cloisite 30B nanocomposite was confirmed by in situ Fourier transform infrared (FTIR) spectroscopy. It was observed via polarized optical microscopy that the liquid crystallinity of PABP in the PABP/Cloisite 30B nanocomposites was more or less intact with a very high degree of dispersion of Cloisite 30B aggregates. Oscillatory shear flow measurements of the organoclay nanocomposites prepared support the conclusions drawn from XRD, TEM, and FTIR spectroscopy.     

Determination of the glass transition temperature of polymer/layered silicate nanocomposites from positron annihilation lifetime measurements

The glass transitions of acrylonitrile-butadiene rubber (NBR)/organoclay nanocomposites with various silicate contents were investigated using positron annihilation lifetime spectroscopy (PALS). The nanocomposites were prepared through melt intercalation of NBR with various concentrations of organoclay (OC30B) modified with the organic modifier, methyl tallow bis(2-hydroxyethyl) quaternary ammonium (MT2EtOH), i.e., Cloisite^® 30B. X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HR-TEM) measurements of the NBR/OC30B nanocomposites showed that the NBR chains were intercalated between the silicate layers, thereby increasing the gallery heights of the organosilicates. The glass transition temperature of NBR was determined using differential scanning calorimetry (DSC). However, it seemed to be very difficult to clearly resolve the very small differences in T_gs caused from various loading of nanosized silicate in NBR/OC30B nanocomposites. Hence, we performed positron annihilation lifetime spectroscopy (PALS) on NBR/OC30B nanocomposites containing various amounts of OC30B (1-10 wt%). Significant changes in the temperature dependencies of free volume parameters (i.e., lifetimes and intensities) were observed at the transition temperature, T_g,PALS, and the T_g,PALS values were found to increase with increasing organoclay content in the samples. These observations are consistent with PALS having a higher sensitivity in the detection of very small changes in free volume properties. The present findings thus highlight the usefulness of PALS for studying phase transition phenomena in polymeric materials with nanoscale structural variations.     

Effect of different nanoparticles on thermal,mechanical and dynamic mechanical properties of hydrogenated nitrile butadiene rubber nanocomposites

Organically modified and unmodified montmorillonite clays (Cloisite NA, Cloisite 30B and Cloisite 15A), sepiolite (Pangel B20) and nanosilica (Aerosil 300) were incorporated into hydrogenated nitrile rubber (HNBR) matrix by solution process in order to study the effect of these nanofillers on thermal, mechanical and dynamic mechanical properties of HNBR. It was found that on addition of only 4 phr of nanofiller to neat HNBR, the temperature at which maximum degradation took place (T_max) increased by 4 to 16°C, while the modulus at 100% elongation and the tensile strength were enhanced by almost 40–60% and 100–300% respectively, depending upon nature of the nanofiller. It was further observed that T_max was the highest in the case of nanosilica‐based nanocomposite with 4 phr of filler loading. The increment of storage modulus was highest for sepiolite‐HNBR and Cloisite 30B‐HNBR nanocomposites at 25°C, while the modulus at 100% elongation was found maximum for sepiolite‐HNBR nanocomposite at the same loading. A similar trend was observed in the case of another grade of HNBR having similar ACN content, but different diene level. The results were explained by x‐ray diffraction, transmission electron microscopy, and atomic force microscopy studies. The above results were further explained with the help of thermodynamics. Effect of different filler loadings (2, 4, 6, 8, and 16 phr) on the properties of HNBR nanocomposites was further investigated. Both thermal as well as mechanical properties were found to be highest at 8 phr of filler loading. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Polybenzoxazine/clay hybrid nanocomposites: influence of preparation method on the curing behavior and properties of polybenzoxazines

Several types of polybenzoxazine/clay hybrid nanocomposites have been prepared from organically modified montmorillonite (OMMT) and mono- or bifunctional benzoxazine, 3-phenyl-3,4-dihydro-2H-1,3-benzoxazine (Pa) or bis(3-phenyl-3,4-dihydro-2H-1,3-benzoxazinyl) isopropane (Ba), respectively. OMMT was prepared by a cation exchange of montmorillonite (MMT) with ammonium salts of amines such as tyramine, phenylethylamine, aminolauric acid, and dodecyl amine. Polybenzoxazine/clay nanocomposites were prepared by two different methods, namely melt method and solvent method. Melt method employs the blending of benzoxazine and OMMT above the melting point of benzoxazine without solvent. In the solvent method, OMMT was dispersed in an organic solvent and then blended with benzoxazine. XRD measurements of the polybenzoxazine/clay hybrid nanocomposites showed that the blending method and the kind of solvent play crucial roles in the dispersion of OMMT in the polybenzoxazine matrix. DSC showed that the inclusion of any type of OMMT significantly lowered the curing exotherm of benzoxazines. The hybrid nanocomposites exhibited higher T_g values than the pristine resins. Dynamic and isothermal TGA clearly showed that the thermal stability was improved by the inclusion of clay.     

Preparation and mechanical properties of PP/PP-g-MA/Org-MMT nanocomposites with different MA content

Summary Polypropylene-clay nanocomposites were prepared by melt intercalation in a twin screw extruder using two mixing methods: two-step mixing and one-step mixing. The effect of using two different kinds of PP-g-MA (polypropylene-grafted maleic anhydride), with graft efficiencies of 0.1 and 1.0 wt% of MA and with different molecular weight, on clay dispersion and mechanical properties of nanocomposites was investigated. Three different clays, natural montmorillonite (Cloisite Na+) and chemically modified clays Cloisite 20A and Cloisite 30B were used. The relative influence of each factor was observed from structural analysis by WAXD, TEM, and mechanical properties. X-ray diffractometry (XRD) was used to investigate the intercalation effect in the nanocomposites. The results indicted that the intercalation effect and mechanical properties, specially modulus, tensile strength and impact strength, were enhanced by increasing the content of MA, using maleated PP with higher graft efficiency, and using the two step mixing conditions. Better dispersion and exfoliation were obtained when using clay 20A than 30B and natural Na+ montmorillonite. The results showed that clay dispersion and interfacial adhesion are greatly affected by the kind of maleated PP. The increase in content of polar groups gives as a result better interfacial adhesion and subsequent mechanical performance.